Isolation of polymerization grade tetrafluoroethylene

ABSTRACT

TETRAFLUOROETHYLENE, INHIBITED FOR STORAGE OR TRANSPORTATION, HAVING A PURITY OF APPROXIMATELY 98 PERCENT IS TREATED BY CONSECUTIVELY CONTACTING WITH SULFURIC ACID, MOLEUCLAR SIEVE AND PYROPHORIC COPPER TO PRODUCE A TETRAFLUOROETHYLENE READILY POLYMERIZABLE TO A POLYTETRAFLUOROETHYLENE OF COMMERICIAL QUALITY. REMOVAL OF TRACE QUANTITIES OF POLYMERIZATION INHIBITING COMPOUNDS BY PASSAGE OF TREATED TETRAFLUORETHYLENE THROUGH PYROPHORIC COPPER PRODUCES A TETRAFLUOROETHYLENE READILY POLYMERIZABLE TO COMMERICAL QUALITY POLYTETRAFLUORETHYLENE.

United States Patent O 3,804,910 ISOLATION OF POLYMERIZATION GRADE TETRAFLUOROETHYLENE Clarence L. Furrow, Bartlesville, kla., assignor to Phillips Petroleum Company, Bartlesville, Okla.

No Drawing. Continuation-impart of abandoned application Ser. No. 32,735, Apr. 28, 1970. This application Jan. 13, 1972, Ser. No. 217,670

Int. Cl. C07c 21/18 U.S. Cl. 260-6533 8 Claims ABSTRACT OF THE DISCLOSURE BACKGROUND OF INVENTION This application is a continuation-in-part of application Ser. No. 32,735, filed Apr. 28, 1970, now abandoned.

This invention relates to the purification of tetrafluoroethylene. In one of its aspects, it relates to a method for removal of polymerization inhibiting compounds from tetrafluoroethylene. In another of its aspects, it relates to the removal of trace quantities of polymerization inhibiting compounds from tetrafluoroethylene. In still another of its aspects, it relates to the production of tetrafiuoroethylene that can be readily polymerized into commercial molding grade polytetrafluoroethylene.

In one concept of the invention, it provides a method for removing inhibiting compounds from tetrafluoroethylene by contacting the tetrafluoroethylene containing polymerization inhibitors with a series of treating com pounds. In another of its concepts, the invention provides for reducing the quantity of polymerization inhibiting compounds present in tetrafluoroethylene by passing tetrafluoroethylene previously treated to reduce inhibiting compound concentration through pyrophoric copper to produce tetrafluoroethylene that can be polymerized to commercial molding grade polytetrafluoroethylene.

Since the attractive qualities of polytetrafiuoroethylene occur only at very high molecular weight any impurities capable of end-capping a growing chain or capable of causing chain transfer or otherwise inhibiting chain growth to a very high molecular weight must be rigorously excluded from tetrafluoroethylene which is to be polymerized. The preparation of commercially desirable high molecular weight polymer requires the use of an unusually pure tetrafluoroethylene. It is necessary that tetrafiuoro ethylene of high purity be used initially in the polymerization because the nonwettable, insoluble nature of polytetrafiuoroethylene restricts work-up possibilities. This requirement of initially high purity tetrafluoroethylene has caused the industrial practice of polymerizing uninhibited tetrafluoroethylene because, once inhibited, it has been impractical by previously known methods to subsequently purify tetrafluoroethylene sutficiently for polymerization Patented Apr. 16, 1974 to commercial quality polytetrafluoroethylene. Up to now closely coordinated monomer and polymer facilities have generally been required. The use of the present invention makes practical the inhibition of tetrafluoroethylene prior to polymerization with a consequent reduction in the hazards of tetrafluoroethylene manipulation and increased flexibility in plant operation.

Various methods for treating tetrafluoroethylene for the removal of impurities are known to the art. U.S. Pat. 3,218,364 teaches the treatment of fluoroolefin monomer with an aqueous solution of sulfuric acid to remove from the monomer those olefinic impurities which tend to decrease the thermal stability of any polymer produced from such a fluoroolefin. U.S. Pat. 3,215,747 teaches that trifluoroethylene can be separated from tetrafluoroethylene by the selective adsorption of the trifiuoroethylene on Linde Molecular Sieves Type 10X. A method forremoval of oxygen from tetrafluoroethylene by passing a gas over a metallic catalyst, such as copper or nickel, at elevated temperature is disclosed in U.S. Pat. 2,407,405. All of these methods provide for removal of specific compounds, but the exhaustive treatment necessary using any one of these methods makes their use impractical for purification of tetrafluoroethylene to the degree necessary for commercial grade polytetrafluoroethylene production. It has been observed that grossly removing the polymerization inhibitor and impurities present in tetrafluoroethylene by contacting the tetrafluoroethylene with sulfuric acid and then with molecular sieve produces a tetrafluoroethylene stream which can then be raised to the abnormally high tetrafluoroethylene purity required for production of polytetrafluoroethylene of commercial quality by contacting the partially purified stream with pyrophoric copper. This 3-component purification train is elfective, economical and dependable. The three stages are necessary because passage of the stream through pyrophoric copper without grossly removing the inhibiting compounds would require impractically large quantities of pyrophoric copper. This invention provides a method for purifying inhibited tetrafluoroethylene to the extent required for production for polytetrafiuoroethylene of commercial quality which has until now been unknown to the art.

It is therefore an object of this invention to provide a method for producing tetrafluoroethylene which can be readily polymerized into polytetrafluoroethylene of commercial grade. It is another object of this invention to provide an economical, safe and eflicient method for removing polymerization inhibitor from tetrafluoroethylene.

Other aspects, concepts, and objects are apparent from a study of this disclosure and the appended claims.

SUMMARY OF INVENTION According to the present invention there is provided a method for the removal of polymerization inhibiting compounds from tetrafluoroethylene containin the same, the

' inhibiting compounds tending otherwise to prevent polymstream which is treated by contacting with pyrophoric copper to increase the purity of the tetrafluoroethylene to the level required for production of polytetrafluoroethylene of commercial quality.

1 purified stream is then passed across pyrophoric copper to'increase the purity of the tetrafiuoroethylene stream to the level required for production of polytetrafluoroethylcm of commercial quality.

In accordance with this invention, a stream of tetrafiuoroethylene containing polymerization inhibitor is passed from any source, which can be storage or shipment containers or a production source, into contact with sulfuric acid. This contacting can be by bubbling the tetrafluoroethylene through a fixed bath of the acid or countercurrent flow of tetrafiuoroethylene through a fiow of the -acid either with or without a solid material interposed to .break up the flow patterns or by any other contacting -means assuring intimate contact of the tetrafiuoroethylene and the sulfuric acid. The effiuent tetrafiuoroethylene .stream is then passed through a bed of molecular sieve in such a manner that intimate contact between the tetrafiuoroethylene and molecular sieve is achieved. The tetrafluoroethylene is then intimately contacted with pyrophoric copper. The contact can be by any of the means already well known. The efiluent tetrafiuoroethylene is purified of polymerization inhibiting compounds to the degree necessary to produce commercially acceptable polytetrafiuoroethylene of commercial molding grade.

Throughout this application polytetrafiuoroethylene of commercial quality is defined as material that will meet current ASTM D1457-62T specifications for general purpose molding resin. This specification is outlined below in comparison Table I. Sulfuric acid treatment removes not only side products of tetrafiuoroethylene preparation such as trifiuoroethylene and difluoroethylene but also terpene hydrocarbon mixtures which are often added to tetrafiuoroethylene as polymerization inhibitor. Efiicient sulfuric acid scrubbing at the beginning of the purification train will minimize the purification that must be done downstream by molecular sieve and pyrophoric copper thus postponing the need for regenerating these elements .of-the train. Therefore, a unit consisting of multiple scrubbers in series is more desirable than a single sulfuric acid scrubber. Since the acid darkens with absorption of polymerization inhibiting compounds visual inspection of Ceramic, glass or other inert substance is the preferred material of construction to preclude possible evolution of hydrogen bycontact of the acid with metal.

The tetrafiuoroethylene suitable for purification by the methodv of this invention is the typical monomer of com meme-which has a minimum purity of about 98.0 weight, ---percent. Usually present are trace amounts of saturated and unsaturated fluorocarbons and oxygen. A polymerizationinhibitor such as limonene is always added in quantities of up to about l weight percent to prevent premature in U.S. Pats. 2,882,243 and 2,882,244 are particularly suitable for use in this invention. Absorbents of vthese types are commercially available. Absorbents used in this invention should have pore openings with an effective pore diameter of at least about 5 A. Absorbents with pore openings up to about 10 A have been proved effective. The Linde Molecular Sieve 10X having an effective pore size of about 8 A. has been found to be particularly effective.

The last element of the purification train is a treatment column containing pyrophoric copper. The effectiveness of pyrophoric copper in removing oxygen is well known. Oxygen can inhibit tetrafiuoroethylene polymerization in certain concentrations, can promote tetrafiuoroethylene polymerization in another range and can form explosive mixtures in certain concentrations with tetrafiuoroethylene. The inclusion of pyrophoric copper has an added benefit of assuring the removal of traces of oxygen from a tetrafiuoroethylene system. The removal of traces of other compounds capable of inhibiting the production of exceptionally high molecular weight polytetrafluoroethylene could not be accomplished until pyrophoric copper was included in the train, and it is the removal of traces of all inhibiting compounds that permits commercial polytetrafiuoroethylene production.

The pyrophoric copper is placed last in the purification train because its very high reactivity make its use for the removal of gross impurities impractical and because its period of effectiveness between regeneration can thus be increased. The catalyst is effective at room temperature and elevation of temperature is required only for activation and regeneration. In a preferred embodiment activated pyrophoric copper catalyst R3-11 made by Badische Anilin & Soda-Fabrik described in their bulletin B 25% 7.60 is used. The pressure at which the purification is accomplished is dependent only on the driving force needed to produce a preferred flow rate. The purification over pyrophoric copper can be accomplished at ambient temperature and initial reaction temperatures from 20 C.

polymerization of the tetrafiuoroethylene. Amonghthe commercially used polymerization inhibitors for stored or shipped tetrafiuoroethylene are trepinolene, alphapinene and limonene.

Although a wide range of concentrations of sulfuric to C. are practicable.

The following are specific examples showing the purification of tetrafiuoroethylene and its subsequent polymerization.

Example I Tetrafluoroethylene, as immediately required for polymerization, was purified by passage at a rate of approximately 1.33 g./min. through a 40-55 micron frit into concentrated sulfuric acid, followed by 10X molecular sieve (133 g. in 0.5 inch stainless steel tubing) and finally through Badische R3-1l (32 g. 20/40 mesh in 0.25 inch stainless steel tubing). The purified tetrafiuoroethylene was condensed at Dry Ice temperature in a ballast cylinder which was then used, upon removal of cooling, as supply source for the polymerization reaction.

Example If Sodium bisulfite (0.00125 g.), potassium persulfate (0.0025 g.), deoxygenated water (500 ml.) and tetrafluoroethylene (190-200 p.s.i.g.) were charged in the ab sence of air to a stirred, l-liter autoclave. Polymerization proceeded at '60-65 C. by adding additional tetrafiuoroethylene as required to maintain 190-200 p.s.i.g. The polymerization was terminated after 56 min. by venting the autoclave. The polymer (61.2 g.) was vigorously washed with deionized water and dried for 24 hrs. at 100 C./ reduced pressure.

' The real, best and ultimate test of tetrafiuoroethylene monomer purity is the quality of the resulting polytetrafluoroethylene. Although the production of high quality acid can be used to treat a tetrafiuoroethylene monomer advantageous results can be obtained using aqueous solupreferably in a range from about 90 to about 98 percent by weight.

The type of synthetic zeolite molecular sieves described polymer normally'necessitates the use of high purity monomer, this is particularly true of polytetrafluoroethylene because of the exceptionally high molecular weights need to afford the properties commercially desirable. The level of polymer quality, therefore, amounts to a more sensitive and exacting test of monomer purity than analytical methods provide. The data presented in Table I below was compiled from samples purified and polymerized as described in the examples above. This data points out the efiectiveness of the three stage purification with an aqueous solution of at least 50 percent sulfuric acid, molecular sieve having an effective pore diameter of at least 5 A. and pyrophoric copper thereby removing train as compared to purification without the pyrophoric 5 polymerization inhibiting compounds.

copper purification step.

2. The method of claim 1 wherein tetrafiuoroethylene TABLE II Concentration, p.p.m.

Llmon- TFE CzFsH Y 1 Cycle-E ene 5 Sample source 4 99. 8 1. 83 1. 36 2, 240 470 Cylinder. 99. 8 0 0 2, 160 0 Purification train exit.

1 Normalized to MM p.p.m. (limonene not determined) obtained by "Aerograph 1520" analysis.

1 Unidentified.

' Cone, p.p.m. obtained in independent sample.

4 Rounded off to nearest tenth.

Reasonable variation and modification are possible withi the scope of the foregoing disclosure and the appended claims to the invention, the essence of which is that there has been provided a method for effectively reducing the level of polymerization inhibiting compounds in a tetrafiuoroethylene monomer stream by contacting the monomer in a three-stage purification train successively with concentrated sulfuric acid and molecular sieve to produce a monomer stream which is then contacted with pyrophoric copper to produce a monomer of sufficient purity to readily polymerize into polytetrafluoroethylene of commercial molding grade.

I claim:

1. A method for treating tetrafluoroethylene comprising successively intimately contacting tetrafluoroethylene of about 98 weight percent purity is contacted successively with said sulfuric acid and said molecular sieve whereby polymerization inhibiting compounds are grossly removed and said tetrafluoroethylene is then contacted with pyrophoric copper to remove trace quantities of said polymerization inhibiting compounds.

3. The method of claim 1 wherein the initial reaction temperature of the tetrafiuoroethylene and the pyrophoric copper is in the range of about 20 C. to about C.

4. The method of claim 3 wherein purification is accomplished at ambient temperature.

5. The method of claim 3 wherein the concentration of sulfuric acid is in the range of about 50 to about 98 percent by weight and the pore diameters of the molecular sieves are about 5 A to about 10 A.

6. The method of claim 2 wherein the concentration of sulfuric acid is in the range of about 50 to about 98 percent by weight and the pore diameters of the molecular sieves are about 5 A to about 10 A.

7. The method of claim 5 wherein the concentration of the sulfuric acid is in the range of about to about 98 percent by weight and the pore diameters of the molecular sieves are about 8 A.

8. The method of claim 6 wherein the concentration of sulfuric acid is in the range of about 90 to about 98 percent by weight and the pore diameters of the molecular sieves are about 8 A.

References Cited UNITED STATES PATENTS 2,917,556 12/ 1959 Percival 260-6533 3,215,747 11/1965 Fainberg et al. 260-6533 3,218,364 11/1965 Kometani et al. 260-6533 DANIEL D. HORWITZ, Primary Examiner 

